Cellulose terpolymer textiles

ABSTRACT

Fibrous cellulose-terpolymers with was-wear properties have been produced by a process comprising a series of steps consisting of irradiation of the substrate with gamma radiation, reaction with a first monomer (monomer A) to form a copolymer, irradiation of the copolymer, and reaction with a second monomer (monomer B) to produce the terpolymer of cellulose-poly(monomer A)-poly(monomer B).

United States Patent 1191 Mares et al.

[ Dec. 16, 1975 CELLULOSE TERPOLYMER TEXTILES [75] Inventors: Trinidad Mares; Jett Clinton Arthur, both of New Orleans, La.

[73] Assignee: The United States of America as represented by the Secretary of Agriculture, Washington, DC.

[22] Filed: Oct. 10, 1973 [21] Appl. No.: 404,978

[52] US. Cl. 8/116 R; 204/159.12; 260/l7.4 CL; 8/193 [51] Int. Cl. D06M 1/00; CO8L 1/00; CO8L 5/00 [58] Field of Search 8/193, 116 R; 204/159.12, 204/l59.l5; 260/17.4 GC, 17.4 CL

[56] References Cited UNITED STATES PATENTS 3,514,385 5/1970 Magat 8/193 3,522,158 7/1970 Garnett 260/l7.4 GC 3,565,780 2/1971 Zimmerman 204/159.12 3,567,606 3/1971 Gupta 204/159.12

3,606,993 9/1971 Arthur 8/193 3,676,207 7/1972 Lofton 8/193 3,687,878 8/1972 lmoto 260/17.4 GC

3,733,257 5/1973 Arthur 204 15912 3,740,362 6/1973 Gaylord 204/15912 3,781,232 12/1973 Gaylord 260/17.4 cc 3,827,858 8/1974 Byrne 8/184 Primary Examiner-Benjamin 1R. Padgett Assistant Examiner-Donald P. Walsh Attorney, Agent, or FirmM. Howard Silverstein; Max D. Hensley [57] ABSTRACT 21 Claims, N0 Drawings CELLULOSE TERPOLYMER TEXTILES FIELD TO WHICH INVENTION RELATES This invention relates to a process for imparting to cotton and other cellulosic textiles selected physical properties with qualities of durable-press textiles, selected surface properties with qualities of soil repellency and release, and selected functional groups permanently introduced on the textiles with qualities of increased chemical reactivity and increased uniformity of dyeability. More specifically, this invention relates to a process for the preparation of a cellulose copolymer which subsequently is copolymerized with a second monomer to yield a fibrous cellulose terpolymer product, the terpolymer product comprising cellulose with two different types of polymers covalently linked to the cellulosic polymeric molecule.

BACKGROUND OF THE INVENTION tion and desorption of textile fabrics, and the like are undesirable effects of making durable-press textile fabrics comprising blending and weaving of different types of textile fibers. Obviously, formation of cellulose terpolymers within the fabric structure of these types of durable-press textile products could improve the soil release, dyeability and uniformity of dyeing and physical properties of the products.

OBJECTIVES OF THE INSTANT INVENTION The main object of this invention is to provide a process for the preparation of cellulosic textile terpolymers with properties which are useful in the production of wash-wear garments and other textile dry goods.

GENERAL ASPECTS OF THE PRESENT INVENTION The instant invention defines a distinct improvement in the reactivity of cotton cellulose by forming a cellulose copolymer and then by reacting the copolymer with a second monomer to yield cellulose terpolymer. For example, it was unexpectedly found that cellulose copolymers were much more easily reacted with a second monomer than if the second monomer was directly reacted with cellulose only. Consequently, the yield of cellulose terpolymer, formed by stepwise reaction of cellulose with monomer to give cellulose copolymer and then reaction of cellulose copolymer with a second monomer, was greater than if reaction of cellulose and two different monomers was attempted simultaneously. Furthermore, the formation of cellulose block copolymers was minimized in the stepwise reactions defined in the instant invention. Factors that apparently effected the increased reactivity of cotton cellulose copolymer during terpolymerization reaction with the second monomer were, as follows: the presence of electronegative groups, such as nitrile and/or carboxyl groups when these groups were substituted on the alpha-carbon of the monomer or on the corresponding carbon of the copolymer; the stability and reactivity of free radicals formed on the cellulosic and/or polymeric parts of the cellulose copolymer with other monomers. That is, during the terpolymerization reaction, the second monomer may terpolymerize with cellulose and/or the polymer of the cellulose copolymer.

PHILOSOPHY AND SPECIFIC ASPECTS OF THE PRESENT INVENTION The source of cellulose in the preparation of cellulose terpolymers was commercial grey cotton sateen fabric, about 7.5 ounces per square yard, that had been enzymatically desized, alkali scoured, and peroxide bleached on a pilot plant scale. Samples of the cotton sateen fabric were dried over phosphorus pentoxide under vacuum at 25C for 16 hours to yield a fabric with a moisture content of about 0.5 percent. The drying step was not essential to the process of this invention; however, the yield of product was increased if the cotton sateen fabric was initially dried. Then the dried cotton sateen fabric was irradiated by exposure of the fabric to gamma radiation from cobalt-60, a convenient source of high-energy radiation, while in a nitrogen atmosphere and at 25C to a dosage of about 0.5 megarad, thereby producing an activated cotton sateen fabric containing long-lived free radicals on the cellulose molecules of cotton. The exposure of cotton sateen fabric to high-energy radiation was essential to the process of this invention; however, an exact radiation dosage was not required. Generally, the extent of activation of the cotton sateen fabric, that is, formation of long-lived free radicals on the cellulose molecules of cotton was directly related to the radiation dosage; however, as the radiation dosage given the cotton sateen fabric was increased, prohibitive losses in the natural textile properties of cotton were obtained. At total dosages of one megarad or less, the cotton was activated by formation of long-lived free radicals on the cellulose molecules of cotton, was directly related to the radiation dosage; however, as the radiation dosage given the cotton sateen fabric was increased, prohibitive losses in the natural textile properties of cotton were obtained. At total dosages of l megarad or less, the cotton was activated by formation of long-lived free radicals on the cellulose molecules of cotton with minimum and acceptable losses in the natural textile prop erties of cotton. Therefore, in the process of this invention in the stepwise preparation of cellulose terpolymers, a total dosage of one megarad or less was used.

Activated cotton sateen fabric (about 1 part by weight), which has been irradiated to a dosage of 0.5 megarad, was immersed at 25C in a vinyl monomer solution (about 1 part by weight of monomer and 8 parts by weight of solvent) that had been purged free of oxygen by flushing with nitrogen for the reaction time of about 60 minutes to give the desired polymer addon. The vinyl monomers were selected from the group which included acrylonitrile, methacrylonitrile, methacrylic acid, acrylic acid, and hexafluoroisopropyl acrylate. A convenient solvent for these monomers was methanol by volume) plus water (20% by volume). A convenient reaction time was one hour. After the desired reaction time, the cotton copolymer fabrics were washed with water, extracted with a solution of methanol (about 80% by volume) and water (about 20% by volume) to remove the unreacted material,

again washed with water, and then air-dried at 25C. Typical polymer add-ons ranged from about 2.6 to 9.4 percent.

Then the cotton copolymer sateen fabrics were dried over phosphorus pentoxide under vacuum at 25C for 16 hours to yield a copolymer fabric with a moisture content of about 0.5 percent. The drying step was not essential to the process of this invention; however, the yield of product was increased if the cotton copolymer sateen fabrics were initially dried. Then the dried cotton copolymer sateen fabric was irradiated by exposure of the fabbric to gamma radiation from cobalt-60, a convenient source of high-energy radiation, while in a nitrogen atmosphere and at 25C to a dosage of about 0.5 megarad, thereby producing an activated cotton copolymer sateen fabric containing long-lived free radicals. The exposure of cotton copolymer sateen fabric to high-energy radiation was essential to the process of this invention; however, an exact radiation dosage was not required. Generally, the extent of activation of the cotton copolymer sateen fabric, that is, formation of long-lived free radicals in the copolymer fabric, was directly related to radiation dosage; however, as the radiation dosage given the cotton copolymer sateen fabric increased, prohibitive losses in the desirable textile properties of the cotton copolymer sateen fabric were obtained. At total dosage of one megarad or less, the cotton copolymer sateen fabric was activated by formation of long-lived free radicals in the copolymer fabric with minimum and acceptable losses in textile properties of the cotton copolymer sateen fabric. The major effects of high-energy radiation on the properties of the cotton copolymer fabric were on the properties of the cotton component of the cotton copolymer fabric. Since the cotton had already been irradiated to a dosage of 0.5 megarad in the process of preparation of the cotton copolymer fabric, the radiation dosage in the step to prepare the cotton terpolymer fabric was limited to 0.5 megarad. Thereby the total radiation dosage to which the cotton was subjected was 1.0 megarad, 0.5 megarad in the process of the copolymer step and 0.5 megarad in the process of the terpolymer step.

Activated cotton copolymer sateen fabric (about 1 part), which had been irradiated to a dosage of 0.5 megarad, was immersed at 25C in a vinyl monomer solution (about 1 part monomer and 8 parts solvent) that had been purged free of oxygen by flushing with nitrogen for the reaction time to give the desired polymer add-on. The vinyl monomers were selected from the group which included acrylonitrile, methacrylonitrile, methacrylic acid, acrylic acid, and hexafluoroisopropyl acrylate. A convenient solvent for these monomers was methanol (80% by volume) plus water (20% by volume). A convenient reaction time was one hour. After the desired reaction time, the cotton terpolymer fabrics were washed with water, extracted with a solution of methanol (about 80% by volume) and water (about 20% by volume) to remove the unreacted material, again washed with water, and then air-dried at 25C. Typical polymer add-ons ranged from about 0.44 to 20 percent.

The following examples are provided to facilitate the comprehension of the invention and should not be construed as limiting the invention in any manner whatsoever.

EXAMPLES A substantial number of samples were prepared by the process of this invention and 26 of these were selected for a chronological tabulation of the results obtained therefrom.

The method of preparation of these terpolymers involved two separate irradiations and reaction periods, thus (1) the immersion of a pre-irradiated (0.5 megarad) dried fabric in an aqueous methanol-monomer (A) solution, reaction at room temperature (25C) under nitrogen for a selected reaction time, usually one hour, followed by extracting in aqueous methanol, washing in water and drying the copolymer fabric, and (2) the dried copolymer was irradiated again (0.5 megarad), then immersed in a second aqueous methanolmonomer (B) solution, reacted exactly under the same conditions as were employed with monomer (A), extracted, washed, and allowed to dry. The unexpected increased reactivity of monomer (B) observed only in the presence of the irradiated cellulose-graftcopolymer (A) was verified for various monomer systerns.

To illustrate the effect of monomer on the polymer add-on in the process for preparation of the cotton sateen copolymer fabrics Examples 1 5 were included, that is: Example 1, acrylonitrile, 2.6% add-on; Example 2, methacrylonitrile, 6.7% add-0n; Example 3, methacrylic acid, 7.4% add-on; Example 4, acrylic acid, 5.2% add-on; and Example 5, hexafluoroisopropyl acrylate, 9.4% add-on.

To illustrate the effect of cotton sateen poly(acrylonitrile) copolymer fabric on the process for the preparation of cotton sateen terpolymer fabrics Examples 6-9 were included. As shown in Examples 6 8 the reactivity of the second monomer was greater with activated cotton sateen poly(acrylonitrile) copolymer fabric than with activated cotton sateen fabric. That is, reactivity of acrylonitrile with copolymer fabric was 3.8% add-on and with fabric, 2.6% add-on; reactivity of methacrylonitrile with copolymer fabric was 7.2% addon and with fabric, 6.7% add-on; and reactivity of hexafluoroisopropyl acrylate with copolymer fabric was 12% add-on and with fabric, 9.4% add-on. As shown in Example 9, if the content of poly(acrylonitrile) in the copolymer fabric was increased from 2.7% add-on to 8.6% add-on, the reactivity of hexafluoroisopropyl acrylate with these activated copolymer fabrics were 12% and 11% add-on, respectively.

TABLE I Ex mpl Monomer Add-on,% Monomer Add-on.%

1 AN 2.6 2 MAN 6.7 3 MAA 7.4

5 FlPA 9.4 6 AN 2.7 AN 38 7 AN 2.7 MAN 72 8 AN 2.7 FlPA l2 9 AN 3.6 FlPA ll 10 MAN 6.7 AN 4.4 ll MAN 6.7 MAA 0.44 12 MAN 6.7 AA 6.9 13 MAN 6.7 FIPA l3 l4 MAA 5.7 FIPA l4 l5 MAA 7.4 AN 3.9 16 MAA 7.4 MAN 7.9 17 MAA 7.4 MAA 7.2 18 MAA 7.4 AA 5.4 l9 FlPA 9.4 AA 5.1

5 TABLE I-continued Effects of Monomer Type and Cellulose Copolymer Composition Cellulose Copolyrner Cellulose Terpolymer Composition Composition Example Monomer Add-on, Monomer" Addon.%

"AN acrylonitrile; MAN methacrylonitrile; MAA methacrylic acid; AA acrylic acid;

FIPA hexafluoroisopropyl acrylate To illustrate the effect of cotton sateen poly(methacrylonitrile) copolymer fabric on the process for the preparation of cotton sateen terpolymer fabrics Examples l 13 were included. As shown in Examples 10, 12, and 13, the reactivity of the second monomer was greater with activated cotton sateen poly(methacrylonitrile) copolymer fabric than with activated cotton sateen fabric. That is, reactivity of acrylonitrile with copolymer fabric was 4.4% add-on and with fabric, 2.6% add-on; reactivity of acrylic acid with copolymer fabric was 6.9% add-on and with fabric, 5.2% add-on; reactivity of hexafluoroisopropyl acrylate with copolymer fabric was 13% add-on and with fabric, 9.4% add-on. As shown in Example 1 l, the reactivity of methacrylic acid with copolymer fabric was 0.44% add-on and with fabric, 7.4% add-on.

To illustrate the effect of cotton sateen poly(methacrylic acid) copolymer fabric on the processes for the preparation of cotton sateen terpolymer fabrics Examples 14 18 were included in the table. As shown in Examples 14 18 the reactivity of the second monomer was equal or greater with activated cotton sateen poly(- methacrylic acid) copolymer fabric than with activated cotton sateen fabric. That is, reactivity of acrylonitrile with copolymer fabric was 3.9% add-on and with fabric, 2.6% add-on; reactivity of hexafluoroisopropyl acrylate with copolymer fabric was 14% add-on and with fabric, 9.4% add-on; reactivity of methacrylonitrile with copolymer fabric was 7.9% add-on and with fabric, 6.7% add-on; reactivity of methacrylic acid with copolymer fabric was 7.2% add-on and with fabric, 7.4% add-on; reactivity of acrylic acid with copolymer fabric was 5.4% add-on and with fabric, 5.2% add-on.

To illustrate the effect of cotton sateen poly(hexafluoroisopropyl acrylate) copolymer fabric on the process for the preparation of cotton sateen terpolymer fabrics Examples 19 and 20 were included in the table. As shown in Examples 19 and 20, the reactivity of acrylic acid with copolymer fabric was 5.1% add-on and with fabric, 5.2% add-on; reactivity of methacrylonitrile with copolymer fabric was 4.1% add-on and with fabric, 6.7% add-on.

To illustrate the effect of cotton sateen poly(acrylic acid) copolymer fabric on the process for the preparation of cotton sateen terpolymer fabrics, Examples 21 26 were included. As shown in Examples 21-23, and 25-26, the reactivity of the second monomer was greater with activated cotton sateen poly( acrylic acid) copolymer fabric than with activated cotton fabric. That is, reactivity of acrylonitrile with copolymer fabric was 3.7% add-on and with fabric, 2.6% add-on; reactivity of methacrylonitrile with copolymer fabric was 8.5% add-on and with fabric, 6.7% add-on. reactivity of methacrylic acid with copolymer fabric was 8.0% addon and with fabric, 7.4% add-on; reactivity of hexafluoroisopropyl acrylate with copolymer fabric was 18-20% add-on and with fabric, 9.4% add-on. As shown in Example 24, reactivity of acrylic acid with copolymer fabric was 3.4% add-on and with fabric, 5.2% add-on.

We claim:

1. A process for preparing a cellulose-terpolymer fibrous textile with wash-Wear properties, the process comprising:

a. impregnating a fibrous cellulosic textile which has been dried to a moisture content below 0.5% and irradiated with gamma radiation to a dosage of about 0.5 megarad for about 60 minutes at room temperature, with an aqueous-methanolic reagent solution, respectively and 20% by volume, Containing a vinyl (A) monomer selected from the group consisting of acrylonitrile, methacrylonitrile, methacrylic acid, acrylic acid, and hexafluoroisopropyl acrylate, said monomer impregnation comprising a reaction condition wherein the charge comprises a part of dried and irradiated cellulosic textile, 1 part of vinyl monomer, and 8 parts of aqueous-methanol, said impregnation constituting a reaction which yields polymer add-ons of about from 2.6% to 9.4%,

b. washing the unreacted reagents off the formed cellulose copolymer with aqueous-methanol,

c. drying the cellulose copolymer to a moisture content of below about 0.5%,

d. irradiating the dried cellulosic copolymer textile product from step (c) with gamma radiation to a dosage of about 0.5 megarad,

e. impregnating the irradiated textile product of (d) with an aqueous-methanolic reagent solution, respectively 80% and 20% by volume, containing a vinyl monomer (B) different than that employed in step (a) and selected from the group consisting of acrylonitrile, methacrylonitrile, methacrylic acid, acrylic acid, and hexafluoroisopropyl acrylate, said monomer impregnation comprising a reaction condition wherein the charge comprises 1 part of dried and irradiated cellulosic textile, 1 part of vinyl monomer, and 8 parts of aqueous-methanol, said impregnation constituting a reaction which yields (B) polymer add-ons of about from 0.44% to 20%, and

f. washing the unreacted reagents off the formed cellulose terpolymer with aqueous-methanol.

2. The process of claim 1 wherein the vinyl (A) monomer is acrylonitrile in step (a).

3. The process of claim 1 wherein the vinyl (A) monomer is methacrylonitrile in step (a).

4. The process of claim 1 wherein the vinyl (A) monomer is methacrylic acid in step (a).

5. The process of claim 1 wherein the vinyl (A) monomer is acrylic acid in step (a).

6. The process of claim 1 wherein the vinyl (A) monomer is hexafluoroisopropyl acrylate is step (a).

7. The process of claim 1 wherein the vinyl (B) monomer is acrylonitrile in step (e).

8. The process of claim 1 wherein the vinyl (B) monomer is methacrylonitrile in step (e).

9. The process of claim 1 wherein the vinyl (B) monomer is methacrylic acid in step (e).

10. The process of claim 1 wherein the vinyl (B) monomer is acrylic acid in step (e).

7 8 ThCPTOCeSS Of Claim 1 wherein the iny 17. The cellulose terpolymer produced by the promonomer 1s hexafluoroisopropyl acrylate in step (e). cess f l i 7,

The Feuulose terpolymer Produced by the P 18. The cellulose terpolymer produced by the process of dam 2. cess f l i 8 lgbggf f gf terpolymer produced by the 19. The cellulose terpolymer produced by the pro- 14. The cellulose terpolymer produced by the process of claim 4.

cess of claim 9.

20. The cellulose terpolymer produced by the pro- 15. The cellulose terpolymer produced by the process of claim cess of claim 5. 10 21. The cellulose terpolymer produced by the pro- 16. The cellulose terpolymer produced by the pro- C655 o a m 1- 

1. A PROCESS FOR PREPARING A CELLULOSE -TERPOLYMER FIBROUS TEXTILE WITH WASH-WEAR PROPERTIES, THE PROCESS COMPRISING: A. IMPREGNATING A FIBROUS CELLULOSIC TEXTILE WHICH HAS BEEN DRIED TO A MOISTURE CONTENT BELOW 0.5% AND IRRADIATED WITH GAMMA RADIATION TO A DOSAGE OF ABOUT 0.5 MEGARAD FOR ABOUT 60 MINUTES AT ROOM TEMPERATURE, WITH AN AQUEOUS-METHANOLIC REAGENT SOLUTION, RESPECTIVELY 80% AND 20% BY VOLUME, CONTAINING A VINYL (A) MONOMER SELECTED FROM THE GROUP CONSISTING OF ACRYLONTRILE, METHACRYLONITRILE, METHACRYLIC ACID, ACRYLIC ACID, AND HEXAFLUOROISOPROPYL ACRYLATE, SAID MONOMER IMPREGNATION COMPRISING A REACTION CONDITION WHEREIN THE CHARGE COMPRISES A PART OF DRIED AN IRRADIATED CELLULOSIC TEXTILE, 1 PART OF VINYL MONOMER, AND 8 PARTS OF AQUEOUS-METHANOL, SAID IMPREGNATION CONSTITUTING A REACTION WHICH YIELDS POLYMER ADDONS OF ABOUT FROM 2.6% TO 9.4%, B. WASHING THE UNREACTED REAGENTS OFF THE FORMED CELLULOSE COPOLYMER WITH AQUEOUS-METHANOL, C. DRYING THE CELLULOSE COPOLYMER TO A MOISTURE CONTENT OF BELOW ABOUT 0.5%, D. IRRADIATING THE DRIED CELLULOSIC COPOLYMER TEXTILE PRODUCT FROM STEP (C) WITH GAMMA RADIATION TO A DOSAGE OF ABOUT 0.5 MEGARADED, E. IMPREGNATING THE IRRADIATION TEXTILE PRODUCT OF (D) WITH AN AQUEOUS-METHANOLIC REAGENT SOLUTION, RESPECTIVELY 80% AND 20% BY VOLUME, CONTAINING A VINYL MONOMER (B) DIFFERENT THAN THAT EMPLOYED IN STEP (A) AND SELECTED FROM THE GROUP CONSISTING OF ACRYLONITRILE, METHACRYLONITRILE, METHACRYLIC ACID, ACRYLIC ACID, AND HEXAFLUOROISOPROPYL ACRYLATE, SAID MONOMER IMPREGNATION COMPRISING A REACTION CONDITION WHEREIN THE CHARGE COMPRISES 1 PART OF DRIED AND IRRADIATED CELLULOSIC TEXTILE, 1 PART OF VINYL MONOMER, AND 8 PARTS OF AQUEOUS-METHANOL, SAID IMPREGNATION CONSTITUTING A REACTION WHICH YIELDS (B) POLYMER ADD-ONS OF BOUT FROM 0.44% TO 20%, AND F. WASHING THE UNREACTED REAGENTS OFF THE FORMED CELLULOSE TERPOLYMER WITH AQUEOUS-METHANOL.
 2. The process of claim 1 wherein the vinyl (A) monomer is acrylonitrile in step (a).
 3. The process of claim 1 wherein the vinyl (A) monomer is methacrylonitrile in step (a).
 4. The process of claim 1 wherein the vinyl (A) monomer is methacrylic acid in step (a).
 5. The process of claim 1 wherein the vinyl (A) monomer is acrylic acid in step (a).
 6. The process of claim 1 wherein the vinyl (A) monomer is hexafluoroisopropyl acrylate is step (a).
 7. The process of claim 1 wherein the vinyl (B) monomer is acrylonitrile in step (e).
 8. The process of claim 1 wherein the vinyl (B) monomer is methacrylonitrile in step (e).
 9. The process of claim 1 wherein the vinyl (B) monomer is methacrylic acid in step (e).
 10. The process of claim 1 wherein the vinyl (B) monomer is acrylic acid in step (e).
 11. The process of claim 1 wherein the vinyl (B) monomer is hexafluoroisopropyl acrylate in step (e).
 12. The cellulose terpolymer produced by the process of claim
 2. 13. The cellulose terpolymer produced by the process of claim
 3. 14. The cellulose terpolymer produced by the process of claim
 4. 15. The cellulose terpolymer produced by the process of claim
 5. 16. The cellulose terpolymer produced by the process of claim
 6. 17. The cellulose terpolymer produced by the process of claim
 7. 18. The cellulose terpolymer produced by the process of claim
 8. 19. The cellulose terpolymer produced by the process of claim
 9. 20. The cellulose terpolymer produced by the process of claim
 10. 21. The cellulose terpolymer produced by the process of claim
 11. 